11 research outputs found

    EVA-Layered Double Hydroxide (Nano)Composites: Mechanism of Fire Retardancy

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    Composites of ethyleneevinyl acetate copolymer with two different layered double hydroxides have been obtained by melt blending and these have been characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, thermogravimetric analysis connected to mass spectroscopy and cone calorimetry. There is some small difference in dispersion between the zinc-containing and the magnesium-containing layered double hydroxides in EVA, but both these are microcomposites with good dispersion at the micrometer level and relatively poor dispersion at the nanometer level. There is a good reduction in the peak heat release rate at 10% LDH loading. In addition to chain stripping, which involves the simultaneous loss of both acetate and a hydrogen atom, forming acetic acid, and the formation of poly(ethylene-co-acetylene), side chain fragmentation of the acetate group also occurs and may be the dominant pathway of thermal degradation in the first step. The presence of the LDH causes acetone, rather than acetic acid, to be evolved in the initial step of the degradation

    Polymer Nanocomposites Using Zinc Aluminum and Magnesium Aluminum Oleate Layered Double Hydroxides: Effects of LDH Divalent Metals on Dispersion, Thermal, Mechanical and Fire Performance in Various Polymers

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    Oleate-containing layered double hydroxides of zinc aluminum (ZnAl) and magnesium aluminum (MgAl) were used to prepare nanocomposites of polyethylene, poly(ethylene-co-butyl acrylate) and poly(methyl methacrylate). The additives and/or their polymer composites were characterized by X-ray diffraction, FTIR, elemental analysis, thermogravimetric analysis, mechanical testing, and cone calorimetry. The unusual packing of the monounsaturated oleate anions in the gallery of these LDHs facilitates the dispersion of these nanomaterials. The inorganic LDH protects the polymer from thermal oxidation, shown by enhancement of the thermal and fire properties of the corresponding polymer nanocomposites. There is a qualitative difference in the morphology of the two LDHs in PE and PMMA. ZnAl is better dispersed in PE while MgAl is better dispersed in PMMA. The zinc-containing material led to a large reduction in the peak heat release rate in polyethylene, while the magnesium-containing material led to enhancement of the fire properties of the more polar poly(methyl methacrylate). These fire properties are consistent with the morphological differences. Neither of these LDHs shows efficacy with poly(ethylene-co-butyl acrylate), which indicates a selective interaction between the LDH and the various polymers

    Material properties of nanoclay PVC composites

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    Nanocomposites of poly(vinyl chloride) have been prepared using both hectorite- and bentonite-based organically-modified clays. The organic modification used is tallow-triethanol-ammonium ion. The morphology of the systems was investigated using X-ray diffraction and transmission electron microscopy and these systems show that true nanocomposites, both intercalated and exfoliated systems, are produced. The mechanical properties have been evaluated and the modulus increases upon nanocomposite formation without a significant decrease in tensile strength or elongation at break. Thermal analysis studies using thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis were conducted. Thermal stability of the PVC systems was assessed using a standard thermal process evaluating the evolution of hydrogen chloride and by color development through the yellowness index. Cone calorimetry was used to measure the fire properties and especially to evaluate smoke evolution. The addition of an appropriately-modified bentonite or hectorite nanoclay leads to both a reduction in the total smoke that is evolved, and an increase in the length of time over which smoke is evolved. Along with this, a reduction in the peak heat release rate is seen. It is likely that the presence of the clay in some way interferes with the cyclization of the conjugated system formed upon HCl loss

    Effect of MgAl-layered double hydroxide exchanged with linear alkyl carboxylates on fire-retardancy of PMMA and PS

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    Alkylcarboxylate-modified layered double hydroxides (LDH) were prepared and used as nanofillers for poly(methyl methacrylate) (PMMA) and polystyrene (PS). The LDH intercalated with long-chain linear alkyl carboxylates (CH3(CH2)nCOO−, n = 8, 10, 12, 14, 16, 20) were prepared via anionic exchange of MgAl–nitrate, showing a systematic increase in basal spacing with longer alkyls. MgAl–undecenoate LDH was prepared by co-precipitation. The MgAl–LDHs were melt blended with poly(methyl methacrylate) and bulk polymerized with styrene to form nanocomposites. The dispersion of the MgAl–LDH in the polymers was investigated by transmission electron microscopy and X-ray diffraction. Thermal and fire properties were studied using cone calorimetry and thermogravimetric analysis; the thermal stability of both polymers was enhanced and a very significant reduction in the peak heat release rate was observed for almost all of the poly(methyl methacrylate) composites and a few of the polystyrene composites

    EVA-layered double hydroxide (nano)composites: Mechanism of fire retardancy. Polymer Degradation and Stability

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    a b s t r a c t Composites of ethyleneevinyl acetate copolymer with two different layered double hydroxides have been obtained by melt blending and these have been characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, thermogravimetric analysis connected to mass spectroscopy and cone calorimetry. There is some small difference in dispersion between the zinc-containing and the magnesium-containing layered double hydroxides in EVA, but both these are microcomposites with good dispersion at the micrometer level and relatively poor dispersion at the nanometer level. There is a good reduction in the peak heat release rate at 10% LDH loading. In addition to chain stripping, which involves the simultaneous loss of both acetate and a hydrogen atom, forming acetic acid, and the formation of poly(ethylene-co-acetylene), side chain fragmentation of the acetate group also occurs and may be the dominant pathway of thermal degradation in the first step. The presence of the LDH causes acetone, rather than acetic acid, to be evolved in the initial step of the degradation

    Polymer nanocomposites using zinc aluminum and magnesium aluminum oleate layered double hydroxides: Effects of the polymeric compatibilizer and of composition on the thermal and fire properties of PP/LDH nanocomposites

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    A series of five oleate-containing layered double hydroxides with varied ratios of zinc to magnesium, i.e., with the general formula Zn2−yMgyAl(OH)6 [CH3(CH2)7CHCH(CH2)7COO]·nH2O, were synthesized and used to prepare nanocomposites of polypropylene (PP). The nanomaterials were characterized by elemental analysis, attenuated total reflection-infrared spectroscopy (ATR-IR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA), while the composites were characterized by XRD, TGA, transmission electron microscopy (TEM) and cone calorimetry. The zinc-containing LDH showed better dispersion in the polymer at the micrometer level than did the magnesium-containing LDH while both are equally well-dispersed at the nanometer level. The magnesium-containing composites led to more thermally stable systems in TGA experiments, while the zinc systems gave greater reductions in heat release rate during combustion. Dispersion was also affected by the amount of PP-g-MA which was present. More PP-g-MA gave better dispersion and a significantly reduced peak heat release rate, i.e., enhanced fire performance

    Transposable elements in phytopathogenic Verticillium spp.: insights into genome evolution and inter- and intra-specific diversification

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    Background Verticillium dahliae (Vd) and Verticillium albo-atrum (Va) are cosmopolitan soil fungi causing very disruptive vascular diseases on a wide range of crop plants. To date, no sexual stage has been identified in either microorganism suggesting that somatic mutation is a major force in generating genetic diversity. Whole genome comparative analysis of the recently sequenced strains VdLs.17 and VaMs.102 revealed that non-random insertions of transposable elements (TEs) have contributed to the generation of four lineage-specific (LS) regions in VdLs.17. Results We present here a detailed analysis of Class I retrotransposons and Class II “cut-and-paste” DNA elements detected in the sequenced Verticillium genomes. We report also of their distribution in other Vd and Va isolates from various geographic origins. In VdLs.17, we identified and characterized 56 complete retrotransposons of the Gypsy-, Copia- and LINElike types, as well as 34 full-length elements of the “cut-and-paste” superfamilies Tc1/mariner, Activator and Mutator. While Copia and Tc1/mariner were present in multiple identical copies, Activator and Mutator sequences were highly divergent. Most elements comprised complete ORFs, had matching ESTs and showed active transcription in response to stress treatment. Noticeably, we found evidences of repeat-induced point mutation (RIP) only in some of the Gypsy retroelements. While Copia-, Gypsy- and Tc1/mariner-like transposons were prominent, a large variation in presence of the other types of mobile elements was detected in the other Verticillium spp. strains surveyed. In particular, neither complete nor defective “cut-and-paste” TEs were found in VaMs.102. Conclusions Copia-, Gypsy- and Tc1/mariner-like transposons are the most wide-spread TEs in the phytopathogens V. dahliae and V. albo-atrum. In VdLs.17, we identified several retroelements and “cut-and-paste” transposons still potentially active. Some of these elements have undergone diversification and subsequent selective amplification after introgression into the fungal genome. Others, such as the ripped Copias, have been potentially acquired by horizontal transfer. The observed biased TE insertion in gene-rich regions within an individual genome (VdLs.17) and the “patchy” distribution among different strains point to the mobile elements as major generators of Verticillium intra- and inter-specific genomic variation

    Lignin degradation in wood-feeding insects

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    The aromatic polymer lignin protects plants from most forms of microbial attack. Despite the fact that a significant fraction of all lignocellulose degraded passes through arthropod guts, the fate of lignin in these systems is not known. Using tetramethylammonium hydroxide thermochemolysis, we show lignin degradation by two insect species, the Asian longhorned beetle (Anoplophora glabripennis) and the Pacific dampwood termite (Zootermopsis angusticollis). In both the beetle and termite, significant levels of propyl side-chain oxidation (depolymerization) and demethylation of ring methoxyl groups is detected; for the termite, ring hydroxylation is also observed. In addition, culture-independent fungal gut community analysis of A. glabripennis identified a single species of fungus in the Fusarium solani/Nectria haematococca species complex. This is a soft-rot fungus that may be contributing to wood degradation. These results transform our understanding of lignin degradation by wood-feeding insects
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